The recent developments in analytical techniques capable of providing information on the identity and quantity of heteroatom-containing biomolecules are critically discussed. Particular attention is paid to the emerging areas of bioinorganic analysis including: (i) a comprehensive analysis of the entirety of metal and metalloid species within a cell or tissue type (metallomics), (ii) the study of the part of the metallome involving the protein ligands (metalloproteomics), and (iii) the use of a heteroelement, naturally present in a protein or introduced in a tag added by means of derivatisation, for the spotting and quantification of proteins (heteroatom-tagged proteomics). Inductively coupled plasma mass spectrometry (ICP MS), used as detector in chromatography and electrophoresis, and supported by electrospray and MALDI MS, appears as the linchpin analytical technique for these emerging areas. This review focuses on the recent advances in ICP MS in biological speciation analysis including sensitive detection of non-metals, especially of sulfur and phosphorus, couplings to capillary and nanoflow HPLC and capillary electrophoresis, laser ablation ICP MS detection of proteins in gel electrophoresis, and isotope dilution quantification of biomolecules. The paper can be considered as a followup of a previous review by the author on a similar topic (: J. Szpunar, Analyst, 2000, 125, 963).

Advances in analytical methodology for bioinorganic speciation analysis: metallomics, metalloproteomics and heteroatom-tagged proteomics and metabolomics

This focal point review provides an overview of recent developments and capabilities of inductively coupled plasma mass spectrometry (ICP-MS) coupled with different separation techniques for applications in the fields of quantitative environmental and bio-analysis. Over the past years numerous technical improvements, which are highlighted in this review, have helped to promote the evolution of ICP-MS to one of the most versatile tools for elemental quantification. In particular, the benefits and possibilities of using state-of-the-art hyphenated ICP-MS approaches for quantitative analysis are demonstrated with a focus on environmental and bio-analytical applications.

https://journals.sagepub.com/doi/pdf/10.1366/12-06681

Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) for Quantitative Analysis in Environmental and Life Sciences: A Review of Challenges, Solutions, and Trends

Stable isotope labelling methods in mass spectrometry-based quantitative proteomics.

A considerable momentum has recently been gained by in vitro and in vivo studies of interactions of trace elements in biomolecules due to advances in inductively coupled plasma mass spectrometry (ICP MS) used as a detector in chromatography and capillary and planar electrophoresis. The multi-isotopic (including non-metals such as S, P, or Se) detection capability, high sensitivity, tolerance to matrix, and large linearity range regardless of the chemical environment of an analyte make ICP MS a valuable complementary technique to electrospray MS and MALDI MS. This review covers different facets of the recent progress in metal speciation in biochemistry, including probing in vitro interactions between metals and biomolecules, detection, determination, and structural characterization of heteroatom-containing molecules in biological tissues, and protein monitoring and quantification via a heteroelement (S, Se, or P) signal. The application areas include environmental chemistry, plant and animal biochemistry, nutrition, and medicine.

https://analyticalsciencejournals.onlinelibrary.wiley.com/doi/pdf/10.1002/mas.20069

Mass spectrometry in bioinorganic analytical chemistry.

Besides the qualitative analysis of a bio-molecule or even a whole proteome, their quantitative determination is also a topic of growing interest, since only the quantity of proteins or changes in their abundance really reflects the status and changes of a biological system. Various approaches have recently been suggested for the comparative investigation of different sample states resulting in different proteomes (comparative proteomics) on the basis of either relative or absolute protein quantification. These use molecule specific mass spectrometry and stable isotope labels with different chemical properties, which are covalently bound to, or incorporated in vivo into the various protein species within the sample entities compared. Various groups in the field of analytical atomic spectrochemistry have recently been developing new strategies and analytical tools for the complementary implementation of elemental mass spectrometry (e.g. inductively coupled plasma mass spectrometry (ICP-MS)), which is still generally known as only a “metal” detector, in new, “non-traditional” application areas targeting bio-molecular chemistry or even the fast growing field of proteomics related research, which is currently dominated by ESI or MALDI based MS techniques. At this time, three main strategies are emerging for the complementary application of ICP-MS to bio-molecule quantification in life-sciences orientated research. These include (i) the utilisation of natural (hetero) element tags (covalently bound elements e.g. sulfur and phosphorus), which are present in nearly all protein bio-molecules, (ii) the controlled labelling of bio-molecules such as proteins, peptides or antibodys with ICP-MS detectable elements using bi-functional chelating agents (by means of a chemical reaction, which forms a covalent bond between the chelating agent and a specific functional site of the bio-molecule) and (iii) the chemical labelling of bio-molecules with nano-particles which contain elements detectable by ICP-MS. The idea behind all three strategies is to make bio-molecules detectable by ICP-MS and thus benefit from its high sensitivity, linearity and matrix robustness. This would allow the qualitative detection and quantitative determination of nearly all bio-molecules provided the stoichiometry of either the natural tag or the chemical label is known. This article will give a critical review of the latest developments in the field of quantitative proteomics and will highlight key applications of ICP-MS as a complementary tool to ESI or MALDI MS techniques for selected proteomics or biochemistry related applications. Special emphasis is placed on the quantification of bio-molecules using elements that are covalently bound to proteins or peptides and which show wide distributions in these bio-molecules as tags.

Chemical labels and natural element tags for the quantitative analysis of bio-molecules

A sensitive and highly selective methodology for the determination of a wide range of pesticides, based on the simultaneous element-specific determination of phosphorus, sulfur, chloride, bromine and iodine by gas chromatography hyphenated with octopole reaction cell-inductively coupled plasma mass spectrometry (GC-CC-ICP-MS) is described. The chromatographic system was optimised for separation efficiency and short run times and was coupled via a commercially available interface with an octopole reaction cell ICP-MS system which is equipped with an on-axis collision cell. Instrumental settings were optimised with respect to high sensitivity for the target nuclides 31P, 32S, 35Cl, 79Br and 127I and minimized background levels especially for the ions most affected by interferences, such as 31P+, 32S+. Helium and nitrogen were tested as additional plasma gases for possible sensitivity enhancement of the element-specific detection resulting from improved ionisation processes inside the plasma. Due to the multi-element capability of the instrumental setup and the good accuracy of the retention times that were achieved, identification of the detected pesticides can be carried out using their retention times, the element compositions and element ratios present in each chromatographic peak. For the different pesticides detection limits down to the ppt level or the low ppb level were obtained. The average RSDs of the retention times and the peak areas were better than 0.8% and 8%, respectively. The analytical methodology developed has been applied to the screening of different fruit extracts for pesticides. Peaks were identified by comparison of the retention times obtained and by their elemental composition. Quantitative results have been obtained both by external calibration and by using a compound independent calibration.

Sensitive, simultaneous determination of P, S, Cl, Br and I containing pesticides in environmental samples by GC hyphenated with collision-cell ICP-MS

By combining recent advances in inductively coupled plasma mass spectrometry (ICP-MS) technology including improved collision cell efficiency, aerosol dilution and discrete sampling, a rare synergy has been achieved resulting in a system that is not only much faster than previous instruments, but also shows improved ease of use and superior matrix tolerance. This work demonstrates the benefits of such a system by demonstrating United States Environmental Protection Agency (USEPA) compliant analysis of a range of high matrix certified reference materials for 26 elements in less than 2 minutes per sample.

/pdf/combining-helium-collision-mode-aerosol-dilution-and-2qm5wugesm.pdf

Combining Helium Collision Mode, Aerosol Dilution and Discrete Sampling to Maximize Matrix Tolerance and Productivity in ICP-MS Analysis of Environmental Samples

Steven M. Wilbur

Papers

Sensitive, simultaneous determination of P, S, Cl, Br and I containing pesticides in environmental samples by GC hyphenated with collision-cell ICP-MS

Combining Helium Collision Mode, Aerosol Dilution and Discrete Sampling to Maximize Matrix Tolerance and Productivity in ICP-MS Analysis of Environmental Samples